Oxygen impermeable leak free container

ABSTRACT

The present invention relates to an improved container for food and non-food products. The container utilizes a novel paperboard barrier laminate structure which maintains an isolated gas environment in the container. The laminate makes use of high strength, heat-resistant and caulking polymer layers which prevent pinholes, cuts, or cracking of the barrier layers during blank conversion, package formation, and package distribution. In addition, the novel polymer resin layers act to caulk the seams and channels present in the carton providing a sealed leak free container.

BACKGROUND OF THE INVENTION

The invention relates to a heat-sealable barrier laminate structurewhich produces an oxygen impermeable, leak free container. Moreparticularly, this invention relates to barrier laminate structureswhich are comprised of specific high strength polymer resin layers whicheffectively prevent heat activation pinholes, cuts or cracking of oxygenbarrier layers caused during scoring and especially during folding andheat sealing of the laminate in package formation.

The invention as disclosed and claimed herein is closely related topending application Ser. Nos. 191,987; 191,988 now U.S. Pat. No.4,888,222; Ser. No. 191,989 now U.S. Pat. No. 4,880,701; Ser. No.191,992 and 191,337 now U.S. Pat. No. 4,859,513, all owned by theAssignee. Also, application Ser. Nos. 354,591 and 354,571 two additionalapplications have been concurrently filed and are related. Thirdly,structures for paperboard containers using heat-sealable polymer resinsand containing various oxygen barrier materials are disclosed in U.S.Pat. Nos. 3,972,467; 4,698,246; 4,701,360; 4,789,575 and 4,806,399, allowned by the Assignee.

Heat-sealable low density polyethylenes are well known to be componentsof current paperboard food and/or non-food packages which provide littlebarrier to the transmission of oxygen. Pinholes, cuts, score line cracksor channels, existent in conventional packaging and cartons, createadditional leakage sites. It is well known that impermeable materialssuch as aluminum foil, polar brittle materials such as:polyacrylonitriles,polyvinylidenechlorides, polyvinyl chlorides, etc.,provide varying degrees of barrier to the transfer of oxygen. However,all these materials lack the requisite strength at high rates ofdeformation, namely stress cracking resistance during scoring, packageformation and distribution abuse to provide a resultant oxygenimpermeable and airtight structure. In addition, leakage through theuncaulked channels of the carton in the top, bottom and side seam havelikewise resulted in poor whole carton oxygen barrier properties.

The existing commercial structures for a paperboard carton for liquidand solid, food and non-food, products have utilized an easilyheat-sealable barrier laminate composed of a paperboard substrate and afoil oxygen barrier layer, both being sandwiched between two thicklayers of low density polyethylene (LDPE). The LDPE is a relativelyinexpensive heat-sealable moisture barrier material. The conventionalstructure falters in that the foil layer which acts as the barrier tothe transmission of oxygen in and out of the carton cracks during blankconversion, carton formation, and package distribution stages.

Bending and folding occurring during the formation of a gable "type"top, flat "type" top, or other folded, heat-sealed top closure, and afin-sealed, or other conventional folded bottom puts excessive amountsof local stress on the thin foil and/or other oxygen barrier layer and,as typically results, cracks and pinholes appear.

To date, there have been no economically attractive commerciallyavailable paperboard packages which consistently approach the oxygenimpermeability of glass or metal containers. The object of the presentinvention is to produce an oxygen impermeable, leak free containerand/or laminate structure such as a paperboard based package or cartonthat prevents the transmission of gases therethrough, and in addition,prevents the escape of flavor components or the ingress of contaminates.A further object of the present invention is to produce such a packagethat is economical on a per-package cost basis, is fundamentallycompatible with existing converting machinery and can be formed, filledand sealed at economically high speeds using conventional packagingmachine temperatures, pressures and dwell times.

Another object of the present invention is to provide this oxygenimpermeable package in a variety of applications including four-ounce to128-ounce containers, or larger, as required by the packager.

A further object of this invention is to incorporate a functionalpolymer layer which exhibits high strength, abuse resistance andtoughness during converting and carton forming in combination withaluminum foil or other oxygen barrier layers and paper, paperboard orother mechanically stable structural material such that thehigh-strength layer reduces the stresses incurred by the barrier layersduring blank conversion, package formation, and distribution.Additionally, should a penetration of the barrier layer or layers occur,the high-strength layer serves to maintain package integrity at thefailure site. The high-strength, heat-resistant layer effectivelyprevents heat activation pinholes through the product contact layer,even when non-foil barrier layers are used.

SUMMARY OF THE INVENTION

A preferred embodiment of the invention reveals an oxygen impermeableleak free barrier laminate, side-seamed blank and/or container providinga total barrier to the loss of essential food flavor oils or non-foodcomponents over an extended product shelf-life as well as an absolutebarrier to the transmission of oxygen during the same extendedshelf-life period. A preferred embodiment of the laminate structurecomprises, from the outer surface to the inner surface, contacting theessential oils, flavors and/or components of food or non-food products:an exterior layer of a low density polyethylene, a mechanically stablestructural substrate, such as an unbleached or bleached paper orpaperboard material, a corrugated board, a stiff polymer resin materialsuch as high density polyethylene or polypropylene, or multi-plycombinations thereof, a first layer of a caulking polymer resin such asan ionomer type resin (Surlyn®1652), an oxygen barrier material layersuch as an aluminum foil layer, a sandwich interior layer of anabuse-resistant polymer such as a polyamide type polymer (nylon 6)surrounded by two additional caulking polymer resin layers such as anionomer type resin (Surlyn®1652), and a layer of low densitypolyethylene in contact with the food or non-food product rendering thelaminate structure heat-sealable.

The cartons, side-seamed blanks, or containers constructed of thelaminate of the present invention enable significant containment ofgases in the container as well as preventing any migration of oxygen orcontaminants into the package. The present invention has produced asuitable container which has the ultimate barrier properties. Itutilizes a laminate which can be heat-sealed easily with its exteriorand interior layers being like, non-polar constituents. During theheat-seal processes, the scoring processes, the side-seaming processes,and the folding, forming and filling steps, the particular caulkingpolymer resins, namely ionomer type resins, ethylene acrylic acidcopolymers, ethylene methacrylic acid copolymers, ethylene vinyl acetatecopolymers, ethylene methylacrylate copolymers, polyethylene basedgrafted copolymers and the like, with melt indexes which allow them toflow during the heat-sealing processes (temperatures ranging from 250°F. to 500° F.). The particular selected resins act as a caulking agentto fill the channels produced during formation of the gable, or othertype flat top, the fin-sealed, or other conventional type bottom and theskived side seam. Consequently, each of those gap areas is caulked toprevent the leakage of oxygen therethrough. In addition, the selectionof the particular abuse-resistant polymer, namely polyamide typepolymers, polyester type polymers and ethylene vinyl alcohol copolymersor the like acts to prevent any type of significant deformation damageto the foil or other oxygen barrier layer which would result in a crackor pinhole allowing for the seepage of oxygen therethrough.

The preferred package structures formed from the preferred novellaminates of the present invention not only exhibit these novel oxygenimpermeable and/or other high barrier properties, but the novel laminatestructures are produced using conventional extrusion and/or coextrusioncoating and/or lamination equipment.

The novel laminate structure and materials selected therefor, namely theparticular caulking polymer resins and abuse-resistant polymer resinscontemplated by the present invention, coupled with oxygen impermeableor high oxygen barrier materials, in various combinations, can beutilized in a variety of food or non-food packaging applications.

In one application, the preferred laminate structure is produced usingconventional coextrusion coating equipment.

Secondly, this laminate is printed and forwarded through scoring diesand cutting dies to create flat blanks.

Thirdly, these flat blanks are skived and folded and side-seamed tocreate the side-seamed blanks. During the heat-sealing step of theside-seam operation, the resins which have been selected for theirparticular melt flow characteristics, caulk and seal along the seam.Resins which have melt flow indexes ranging from 4.5 to 14.0 arepreferred. These side-seamed blanks are then forwarded to the particularcustomer for further assemblage.

Fourth, these side-seamed blanks are magazine fed into a machine whereinthey are opened and placed on a mandrel, wherein sealing of the bottomtakes place.

Typically, the bottom folding and sealing is where most of the damage tothe interior thin barrier foil layer occurs in conventional cartons.Utilization of a particular strong polymer resin, comprising anabuse-resistant polymer, such as a polyamide type polymer, preventscracking of the foil layer during the bottom sealing process. The bottomis fully heat-sealed into a flat configuration at which time caulkingpolymer resins, such as ionomer resins, flow in a caulking manner toseal the bottom. The container or package is then forwarded to thefilling step. Next, the top is "prebroken" and filled with theparticular product and then top-sealed. Again, much damage is done tothe foil or other barrier layer during this top-sealing process ofconventional cartons. The utilization of the novel abuse-resistant andcaulking polymer resin constituents in the barrier laminate acts toprevent any damage to the foil or non-foil barrier layer and produce atop closure which has been caulked to doubly prevent any transport ofoxygen.

The novel barrier laminate produced by the present invention not onlyexhibits excellent oxygen barrier properties and can be easilyconstructed, but also meets FDA approval for use in food packaging. Theresins heat seal at low temperatures (250° F. to 500° F.) and thestructures can be converted and cut on conventional machinery.

Thus, until the advent of the present invention, no suitable oxygenimpermeable, leak free containers or packages have been developed whichretain the advantages of using mechanically stable structural substratessuch as paperboard or the like as the base material and FDA approvedheat-sealable barrier layers which are economical and can be producedusing conventional coextrusion coating equipment.

The present invention described herein is particularly useful as acoated paperboard structure employed in the packaging of food andnon-food products. These types of containers make use of a heat-seal forseaming and closing, and are utilized in the formation of folding boxes,square rectangular cartons or containers, or even cylindrical tubes.

In addition, the novel combinations of caulking polymer resins,abuse-resistant polymers and oxygen impermeable and/or high oxygenbarrier materials have other applications as well.

Namely, the combination of high oxygen barrier materials such asethylene vinyl alcohol copolymers or other brittle oxygen barriermaterials coupled with abuse-resistant type polymer resins such aspolyamide type polymers or the like, have applications in combinationwith almost any mechanically stable structural substrate. Particularly,multilayer blow-molded containers incorporating abuse-resistant polymerresins in combination with high oxygen barrier materials is one of thenovel applications of this invention.

One specific example of such an application is the utilization ofethylene vinyl alcohol copolymer in combination with a polyamide typepolymer mounted on a high density polyethylene structural substrate. Thepolyamide type polymer acts to protect the brittle ethylene vinylalcohol copolymer oxygen barrier layer from abuse during shipping andtransport of the overall container structure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional elevation of the preferred embodiment of thelaminate of the present invention;

FIG. 2 is a cross-sectional elevation of an alternate embodiment of thelaminate of the present invention.

FIG. 3 is a cross-sectional elevation of an alternate embodiment of thelaminate of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The preferred embodiment of the invention is for an hermetic, oxygenimpermeable leak free and/or high oxygen barrier leak free packageincorporating a laminate structure as disclosed in FIG. 1. All weightsare expressed in pounds per 3,000 square feet. Disclosed is amechanically stable structural substrate 12 which is most suitably highgrade paperboard stock, for example, 100-300 lbs. or higher sized cartonboard, to which is applied on one side a coating of a low densitypolyethylene polymer 10 in a coating weight of about 12.0 to 30.0 lbs.Layer 10 is the "gloss" layer which contacts the outer atmosphere. Anextrusion coating grade LDPE having a melt flow index ranging from 4.0to 7.0 is suitable for use herein. On the underside or interior portionof the paperboard substrate 12 is coated thereon a layer of a caulkingpolymer resin, 14, such as an ionomer type resin (Surlyn®1652), in acoating weight of about 8.0 to 20.0 lbs., and coated on the interior ofthe caulk is an absolute oxygen impermeable material or a high oxygenbarrier material, such as a 0.000275-0.0005 inch layer of aluminum foilhaving a coating weight of about 12 lbs., 16. Coated onto the foil is asandwich layer, 23, of an abuse-resistant polymer resin such as apolyamide type polymer (nylon 6), 20, in a coating weight of about 3.0to 10.0 lbs., sandwiched between two caulking polymer resin layers, 18and 22, such as an ionomer type resin (Surlyn®1652), in coating weightsof about 2 to 6 lbs., and lastly coated onto the sandwich layer, 23, isa second layer of low density polyethylene polymer 24, in a coatingweight of about 12.0 to 30.0 lbs. rendering the entire laminatestructure heat sealable on conventional heat-seal equipment atconventional heat-seal temperatures (250° F. to 500° F.).

Referring to FIG. 2, an alternate preferred embodiment of the laminateof the present invention is shown. The embodiment adds tie layers aroundthe oxygen barrier material layer to facilitate better adhesion in thestructure. In this alternate preferred embodiment, the mechanicallystable structural substrate 28, such as a paperboard substrate, having aweight of 100-300 lbs. or higher for a half pint or smaller, pint,quart, half gallon, gallon and multi-layer structures, has extrusioncoated on its external surface a 12.0 to 30.0 lb. layer of a low densitypolyethylene polymer 26. On the internal surface of the mechanicallystable structural substrate 28, is applied a first sandwich layer 33, ofan oxygen barrier material such as an ethylene vinyl alcohol copolymer,having a coating weight of about 8.0 to 20.0 lbs., 32, sandwichedbetween two tie layers, 30 and 34, such as a Plexar®175, having coatingweights of about 2.0 to 6.0 lbs. each. Coated onto the first sandwichlayer 33 is a second sandwich layer 39 comprising an abuse-resistantpolymer resin, such as a polyamide-type polymer (nylon 6), 38, having acoating weight of about 3.0 to 10.0 lbs. sandwiched between two caulkingpolymer resin layers, 36 and 40, having coating weights of about 2.0 to6.0 lbs. each. Finally, coated thereon, is a 12.0 to 30.0 lb. layer of alow density polyethylene polymer 42 which in combination with layer 26renders the entire laminate structure heat-sealable.

FIG. 3 is another preferred embodiment of the present invention. Amechanically stable structural substrate such as a paperboard substratehaving a weight of 100-300 lbs., or higher, 46, is coated with a 12.0 to30.0 lb. layer of a low density polyethylene polymer on its exterior 44.On the interior layer of the substrate 46 is coated a five-layersandwich, 51, having the following laminate structure: A first 2.0 to6.0 lb. layer of a caulking resin material, such as an ionomer resin(Surlyn®1652), 48, a first 3.0 to 10.0 lb. layer of an abuse-resistantpolymer resin, 50, such as a polyamide-type polymer (nylon 6), an oxygenbarrier material layer, 52, such as an ethylene vinyl alcohol copolymer,having a coating weight of about 8.0 to 20.0 lbs., a second 3.0 to 10.0lb. abuse-resistant polymer resin layer, 54, such as a polyamide typepolymer (nylon6), and a second 2.0 to 6.0 lb. caulking polymer resinlayer such as an ionomer resin (Surlyn®1562). Finally coated thereon isa second 12.0 to 30.0 lb. layer of a low density polyethylene polymer,58, rendering the entire laminate structure heat-sealable onconventional heat-seal equipment at conventional heat-seal temperatures.

Although specific coating techniques have been described, anyappropriate technique for applying the layers onto the mechanicallystable structural substrate can be suitably employed, such as extrusioncoating, coextrusion coating, extrusion lamination, coextrusionlamination and/or adhesive lamination of single layer and/or multilayerfilms to the mechanically stable structural substrate to achieve thestated inventions of this patent. The unique effect provided by theoxygen impermeable, leak free packages made from the laminate of thepresent invention is clearly demonstrated by the following Examplesoutlined in Table I. The preferred embodiment of the present inventionis listed as the "International Paper oxygen impermeable halfgallon" andit utilizes as its mechanically stable structural substrate a 282 lb.layer of paperboard. The preferred structure is compared in Table I to avariety of commercial paperboard based and non-paperboard basedcontainers currently available in the market place and recommended forextended shelf-life applications.

                                      TABLE I                                     __________________________________________________________________________    Average Whole Container Oxygen Transmission Rates (OTR)                                                     OTR (CC/M.sup.2 /Day)                                             Avg., CC O.sub.2 /Pkg./Day                                                                To Fill -                                       Container         (75° F., 50% RH, in Air)                                                           Volume (ml) Ratio*                              __________________________________________________________________________    INTERNATIONAL PAPER                                                                              0.000       0.000                                          (OXYGEN IMPERMEABLE                                                           HALF-GALLON)                                                                  TOPPAN, EP-PAK (1500 ml)                                                                         0.005       0.004                                          WITH PLASTIC FITMENT                                                          INTERNATIONAL PAPER                                                                              0.016      0.2                                             ASEPTIC (250 ml.)                                                             TETRA BRIK-PAK (250 ml.)                                                                         0.013      0.2                                             CAPRI-SUN POUCH   0.01        0.3                                             (200 ml.)                                                                     TREESWEET COMPOSITE                                                                             0.29        0.4                                             FIBER CAN (1360 ml.)                                                          CONOFFAST CUP      0.022      0.4                                             (250 ml.)                                                                     INTERNATIONAL PAPER                                                                             1.11        0.5                                             HOT FILL (2000 ml.)                                                           GALLON HDPE       2.75        0.5                                             (BLOW MOLDED BOTTLE)                                                          HALF-GALLON HDPE  1.98        1.1                                             (BLOW MOLDED BOTTLE)                                                          HYPAPAK (700 ml.) 0.52        1.7                                             HAWAIAN PUNCH COMPOSITE                                                                         0.09        2.0                                             CAN (236 ml.)                                                                 COMBIBLOCK (250 ml.)                                                                            0.21        3.2                                             JUICE BOWL COMPOSITE                                                                            0.34        4.1                                             CAN (355 ml.)                                                                 __________________________________________________________________________     *All numbers should be multiplied by 10.sup.-2                           

It can be seen that the container prepared from a laminate of thepresent invention provides a complete hermetic barrier to the transportof oxygen.

The specially selected abuse-resistant polymer constituents such as thepolyamide type polymers which make up the container are resilient enoughto prevent any type of cutting, pinholing, or other damage caused duringthe converting, carton formation and distribution steps. In addition,the container utilizes ionomer type resins as caulking material for thechannels and seams.

The mechanically stable structural substrate may consist of anunbleached or bleached paper or paperboard material, a corrugated typeboard material, a stiff polymer resin material such as high densitypolyethylene or polypropylene, and/or multi-ply combinations thereof.

The barrier layer may consist of an aluminum foil, an ethylene vinylalcohol copolymer, a polyvinyl alcohol polymer, a polyethyleneterephthalate, a polybutylene terephthalate, a glycol-modifiedpolyethylene terephthalate, an acid-modified polyethylene terephthalate,a vinylidene chloride copolymer, a polyvinyl chloride polymer, a vinylchloride copolymer, a polyamide polymer or a polyamide copolymer, orcombinations of these materials.

The heat-sealable outer and inner polymer layers may consist of a lowdensity polyethylene polymer, a linear low density polyethylene polymer,a medium density polyethylene polymer and/or blends thereof. Theheat-sealable polymer materials contemplated for this invention allpossess FDA approval for food contact applications and all have theability to heat-seal on conventional equipment at conventional heat-sealtemperatures (250° F. to 500° F.).

The preferred embodiments of the present invention utilize an aluminumfoil layer as the primary absolute oxygen and flavor oil barriermaterial. All of the above-identified materials could be utilized in allalternate embodiments in place of the foil layer as well as in thepreferred embodiment of the invention. The barrier and high strengthlayers may be applied as film laminations and/or as extrusion coatings.

The invention may be used in materials for all types of blank fed or webfed package forming equipment. The effectiveness of the laminate of thepresent invention as an oxygen impermeable package structure permits asignificant extension of shelf-life of the products packaged in thecontainers.

The tough, high strength, abuse-resistant type materials can be selectedfrom the following group of polymers: polyamide type polymers such asthe preferred Nylon 6, or Nylon 6/66, Nylon 6/12, Nylon 6/9, Nylon 6/10,Nylon 11, Nylon 12; polyethylene terephthalate; polybutyleneterephthalate; and ethylene vinyl alcohol copolymers; or other similartough, high strength polymeric materials which have tensile strengths of10,000 psi or greater at conventional heat-seal temperatures (250° F. to500° F.).

In addition, the high strength, low viscosity caulking resins preferredare selected from the following group of polymers: ionomer type resins,such as the preferred zinc or sodium salts of ethylene methacrylic acid(Surlyn®1652 or the like); ethylene acrylic acid copolymers; ethylenemethacrylic acid copolymers; ethylene vinyl acetate copolymers; ethylenemethylacrylate copolymers, ethylene based graft copolymers; and thelike, all exhibiting melt flow indexes ranging from 4.5 to 14.0.

Adhesive tie layers preferred are selected from the following: Plexars®from Quantum Chemical Co., more commonly known in the industry asethylene based graft copolymers; CXA's® from Dupont, more commonly knownin the industry as modified polyethylene resin containing vinyl acetate,acrylate and methacrylate comonomers; Admer's® from Mitsui, morecommonly known in the industry as polyethylene copolymer based materialswith grafted functional groups, and similar performing tie resins.

Additional abuse-resistant polymers, caulking polymer resins,mechanically stable structural substrates, oxygen barrier materials, andadhesive tie layers which meet the specifications and requirementsoutlined above could also be utilized to practice the present invention.

This invention provides a means of transforming the economical, highvolume, gable top or flat top paperboard or non-paperboard food/non-foodcarton into an oxygen impermeable, leak free package that can beproduced, sold, and filled economically at high production speeds,offering a low-cost hermetic packaging alternative to glass and metal,with the bulk of one embodiment of the package being biodegradablepaperboard from a renewable resource.

The novel container has the feature of acting as a stand aloneabuse-resistant package for products which when contained in normalpackaging are considered to be extremely difficult to contain. Suchproducts include: detergents, synthetic sweeteners, oil products, etc.all of which can be stored in the novel structure embodied by theinvention.

What is claimed is:
 1. An oxygen barrier laminate structure forproducing an oxygen impermeable leak free container comprising:(a) amechanically stable structural substrate having an inner and an outersurface; (b) an outer layer of a heat-sealable polymer material coatedon the outer surface of said mechanically stable structural substrate;(c) a first inner sandwich layer of: a first adhesive tie layer, anoxygen barrier material layer, a second adhesive tie layer, all coatedin the sequence listed on the inner surface of said mechanically stablestructural substrate; (d) a second inner sandwich layer of: a firstcaulking polymer resin layer, an abuse-resistant polymer resin layer, asecond caulking polymer resin layer, all coated in the sequence listedon the inner surface of the second adhesive tie layer of the first innersandwich layer, and; (e) an inner heat-sealable product contact polymermaterial layer of low density polyethylene polymer extrusion coated onsaid inner surface of said second caulking polymer resin layer of saidsecond inner sandwich layer, which is heat-sealable with the outer layerof polymer material on conventional equipment at temperatures rangingfrom 250° F. to 500° F. and wherein said first and second caulkingpolymer resins are selected from the group consisting of zinc salts ofethylene methacrylic acid copolymers, sodium salts of ethylenemethacrylic acid copolymers, ethylene acrylic acid copolymers, ethylenemethacrylic acid copolymers, ethylene vinyl acetate copolymers, ethylenemethacrylate copolymers, and ethylene based graft copolymers.
 2. Anoxygen barrier laminate structure for producing an oxygen impermeableleak free container, said laminate as claimed in claim 1, wherein saidmechanically stable structural substrate is selected from the groupconsisting of bleached paperboard, unbleached paperboard, corrugatedboard, high density polyethylene, high density polypropylene andmulti-ply combinations thereof.
 3. An oxygen barrier laminate structurefor producing an oxygen impermeable leak free container, said laminateas claimed in claim 1, wherein said oxygen barrier material layer isselected from the group consisting of aluminum foil, ethylene vinylalcohol copolymer, polyvinyl alcohol, polyethylene terephthalate,glycol-modified polyethylene terephthalate, acid-modified polyethyleneterephthalate, polybutylene terephthalate, vinylidene chloridecopolymer, polyvinyl chloride polymer, vinyl chloride copolymer,polyamide polymer and polyamide copolymer.
 4. An oxygen barrier laminatestructure for producing an oxygen impermeable leak free container, saidlaminate as claimed in claim 1, wherein said abuse-resistant polymerresin exhibits a tensile strength of 10,000 psi or greater.
 5. An oxygenbarrier laminate structure for producing an oxygen impermeable leak freecontainer, said laminate as claimed in claim 4, wherein saidabuse-resistant polymer is selected from the group consisting ofpolyamide polymers, polyethylene terephthalate, polybutyleneterephthalate and ethylene vinyl alcohol copolymer.
 6. An oxygen barrierlaminate structure for producing an oxygen impermeable leak freecontainer, said laminate as claimed in claim 1, wherein said first andsecond adhesive tie layers are selected from the group consisting ofethylene based copolymers with grafted functional groups, modifiedpolyethylene resin containing vinyl acetate, acrylate and methacrylatecomonomers, and polyethylene copolymer based materials with graftedfunctional groups.
 7. An oxygen barrier laminate structure for producingan oxygen impermeable leak free container, said laminate as claimed inclaim 1, wherein said first and second caulking polymer resins exhibit amelt flow index ranging from 4.5 to 14.0.
 8. An oxygen barrier laminatestructure for producing an oxygen impermeable leak free container, saidlaminate as claimed in claim 1, wherein said mechanically stablestructural substrate is paperboard, said oxygen barrier material layeris aluminum foil, said abuse-resistant polymer resin is a polyamidepolymer having a tensile strength greater than 10,000 psi, and whereinsaid first and second caulking polymer resins are a zinc salt ofethylene methacrylic acid copolymer having a melt flow index rangingfrom 4.5 to 14.0.
 9. An oxygen barrier laminate structure for producingan oxygen impermeable leak free container, said laminate as claimed inclaim 1, wherein said outer and inner heat-sealable polymer material islow density polyethylene, linear low density polyethylene, mediumdensity polyethylene or blends thereof.
 10. An oxygen impermeableside-seamed blank, said blank constructed from a laminate comprising:(a)a mechanically stable structural substrate having an inner and an outersurface; (b) an outer layer of a heat-sealable polymer material coatedon the outer surface of said mechanically stable structural substrate;(c) a first inner sandwich layer of: a first adhesive tie layer, anoxygen barrier material layer, a second adhesive tie layer, all coatedin the sequence listed on the inner surface of said mechanically stablestructural substrate; (d) a second inner sandwich layer of: a firstcaulking polymer resin layer, an abuse-resistant polymer resin layer, asecond caulking polymer resin layer, all coated in the sequence listedon the inner surface of the second adhesive tie layer of the first innersandwich layer, and; (e) an inner heat-sealable product contact polymermaterial layer extrusion coated on said inner surface of said secondcaulking polymer resin layer of said second inner sandwich layer, whichis heat-sealable with the outer layer of polymer material onconventional equipment at temperatures ranging from 250° F. to 500° F.and wherein said first and second caulking polymer resins are selectedfrom the group consisting of zinc salts of ethylene methacrylic acidcopolymers, sodium salts of ethylene methacrylic acid copolymers,ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers,ethylene vinyl acetate copolymers, ethylene methacrylate copolymers andethylene based graft copolymers.
 11. An oxygen impermeable side-seamedblank as claimed in claim 10, wherein said mechanically stablestructural substrate is selected from the group consisting of bleachedpaperboard, unbleached paperboard, corrugated board, high densitypolyethylene, high density polypropylene and multi-ply combinationsthereof.
 12. An oxygen impermeable side-seamed blank as claimed in claim10, wherein said oxygen barrier material layer is selected from thegroup consisting of aluminum foil, ethylene vinyl alcohol copolymer,polyvinyl alcohol, polyethylene terephthalate, glycol-modifiedpolyethylene terephthalate, acid-modified polyethylene terephthalate,polyethylene terephthalate, vinylidene chloride copolymer, polyvinylchloride polymer, vinyl chloride copolymer, polyamide polymer andpolyamide copolymer.
 13. An oxygen impermeable side-seamed blank asclaimed in claim 10, wherein said abuse-resistant polymer resin exhibitsa tensile strength of 10,000 psi or greater.
 14. An oxygen impermeableside-seamed blank as claimed in claim 13, wherein said abuse-resistantpolymer is selected from the group consisting of polyamide polymers,polyethylene terephthalate, polybutylene terephthalate and ethylenevinyl alcohol copolymer.
 15. An oxygen impermeable side-seamed blank asclaimed in claim 10, wherein said first and second adhesive tie layerare selected from the group consisting of ethylene based copolymers withgrafted functional groups, modified polyethylene resin containing vinylacetate, acrylate and methacrylate comonomers and polyethylene copolymerbased materials with grafted functional groups.
 16. An oxygenimpermeable side-seamed blank as claimed in claim 10, wherein said firstand second caulking polymer resins exhibit a melt flow index rangingfrom 4.5 to 14.0.
 17. An oxygen impermeable side-seamed blank as claimedin claim 10, wherein said mechanically stable structural substrate ispaperboard, said oxygen barrier material layer is aluminum foil, saidabuse-resistant polymer resin is a polyamide polymer having a tensilestrength greater than 10,000 psi, and wherein said first and secondcaulking polymer resins are a zinc salt of ethylene methacrylic acidcopolymer having a melt flow index ranging from 4.5 to 14.0.
 18. Anoxygen impermeable side-seamed blank as claimed in claim 10, whereinsaid outer and inner heat-sealable polymer material is low densitypolyethylene, linear low density polyethylene, medium densitypolyethylene or blends thereof.
 19. An oxygen impermeable leak freecontainer, said container constructed from a laminate comprising:(a) amechanically stable structural substrate having an inner and an outersurface; (b) an outer layer of a heat-sealable polymer material coatedon the outer surface of said mechanically stable structural substrate;(c) a first inner layer of caulking polymer resin coated on the innersurface of said mechanically stable structural substrate; (d) a secondinner sandwich layer of: a first caulking polymer resin layer, anabuse-resistant polymer resin layer, a second caulking polymer resinlayer, all coated in the sequence listed on the inner surface of thesecond adhesive tie layer of the first inner sandwich layer, and; (e) aninner heat-sealable product contact layer polymer material extrusioncoated on said inner surface of said second caulking polymer resin layerof said second inner sandwich layer, which is heat-sealable with theouter layer of low density polyethylene polymer on conventionalequipment at temperatures ranging from 250° F. to 500° F. and whereinsaid first and second caulking polymer resins are selected from thegroup consisting of zinc salts of ethylene methacrylic acid copolymers,sodium salts of ethylene methacrylic acid copolymers, ethylene acrylicacid copolymers, ethylene methacrylic acid copolymers, ethylene vinylacetate copolymers, ethylene methacrylate copolymers and ethylene basedgraft copolymers.
 20. An oxygen impermeable leak free container, asclaimed in claim 19, wherein said mechanically stable structuralsubstrate is selected from the group consisting of bleached paperboard,unbleached paperboard, corrugated board, high density polyethylene, highdensity polypropylene and multi-ply combinations thereof.
 21. An oxygenimpermeable leak free container, as claimed in claim 19, wherein saidoxygen barrier material layer is selected from the group consisting ofaluminum foil, ethylene vinyl alcohol copolymer, polyvinyl alcohol,polyethylene terephthalate, glycol-modified polyethylene terephthalate,acid-modified polyethylene terephthalate, polybutylene terephthalate,vinylidene chloride copolymer, polyvinyl chloride polymer, vinylchloride copolymer, polyamide polymer and polyamide copolymer.
 22. Anoxygen impermeable leak free container, as claimed in claim 19, whereinsaid abuse-resistant polymer resin exhibits a tensile strength of 10,000psi or greater.
 23. An oxygen impermeable leak free container, asclaimed in claim 22, wherein said abuse-resistant polymer is selectedfrom the group consisting of polyamide polymers, polyethyleneterephthalate, polybutylene terephthalate, and ethylene vinyl alcoholcopolymer.
 24. An oxygen impermeable leak free container, as claimed inclaim 19, wherein said first and second adhesive tie layers are selectedfrom the group consisting of ethylene based copolymers with graftedfunctional groups, modified polyethylene resin containing vinyl acetate,acrylate and methacrylate monomers and polyethylene copolymer basedmaterials with grafted functional groups.
 25. An oxygen impermeable leakfree container, as claimed in claim 19, wherein said first and secondcaulking polymer resins exhibit a melt flow index ranging from 4.5 to14.0.
 26. An oxygen impermeable leak free container, as claimed in claim19, wherein said mechanically stable structural substrate is paperboard,said oxygen barrier material layer is aluminum foil, saidabuse-resistant polymer resin is a polyamide polymer having a tensilestrength greater than 10,000 psi, and wherein said first and secondcaulking polymer resins are a zinc salt of ethylene methacrylic acidcopolymer having a melt flow index ranging from 4.5 to 14.0.
 27. Anoxygen impermeable leak free container, as claimed in claim 19, whereinsaid outer and inner heat-sealable polymer material is low densitypolyethylene, linear low density polyethylene, medium densitypolyethylene or blends thereof.